Compositions of matter containing epoxy ethers and diamines



Patented Mar. 14, 1950 COMPOSITIONS OF MATTER CONTAINING EPOXY ETHERSAND DIAMINES Theodore 1?. Bradley, Oakland, Calii., asslgnor to ShellDevelopment Company, San Francisco, Calii'., a corporation of DelawareNo Drawing. Application February 28, 1948, Serial No. 12,152

15 Claims. (Cl. 260-47 equivalency greater than one is mixed and reactedwith a saturated aliphatic diamine containing two primary amino groups,one of which is directly linked to a saturated tertiary carbon atom. Inorder to obtain the desired favorable effects, it is essential that thediamine coupling or curing agent contains one primary amino group linkedto a tertiary carbon atom, but the other primary amino group may belinked to a primary, secondary or tertiary carbon atom although it ispreferred that it be linked to a secondary carbon atom. Amongrepresentative diamines which are used in the invention are1,2-diamino-2-methylpropane, 2,3 diamino 2 methylbutane, 2,4-diamino 2methylpentane, 2,3 diamino 2,3-dimethylbutane, 2,5diamino-2,5-dimethylhexane, 3,4-diamino 3,4 dimethylhexane, 2,6 diamino-2,6 dimethylheptane, 2,7-diamino-2,'l-dimethyloctane, etc. The diaminesnecessarily contain at least four carbon atoms, and it is preferred touse those of six to ten carbon atoms. The primary amino groups may belinked to adjacent or vicinal carbon ato or to carbon atoms separated byone or more intervening carbon atoms. The aliphatic diamine has theformula CnH21l(NH2)2 wherein n is an integer of at least 4, andpreferably of 6 to 10.

The compound 2,4-diamino-2-methylpentane is particularly preferred foruse in the invention. For convenience, the compound will be referred toherein by the name diacetone diamine. It may be prepared in thefollowing manner. Acetone and liquid ammonia are heated at 30 C. to 40C. in the presence of about 1 to of concentrated hydrochloric acidwhereby there is formed 2,2,4,4,6 pentamethyltetrahydropyrimidine. Afterseparation from the reaction mixture by distillation, this compoundalong with liquid ammonia in a ratio of 1 to 5 mols per mol of thepyrimidine is heated and reacted at 140 C. to 150 C. in the presence ofa hydrogenation catalyst such as Raney nickel with hydrogen inch.Further details of producing such diamine are disclosed in copendingapplication, Serial No. 736,610, filed March 24, 1947, now Patent No.2,486,648. In like manner, other diamines of this type which are usefulin the invention may be prepared from other lower aliphatic saturatedketones such as methyl ethyl ketone, methyl propyl ketone, diethylketone and the like. Thus, di(methyl ethyl ketone) diamine is preparedby reacting ammonia and methyl ethyl ketone so as to produce a mixtureof the isomers 2,4,5,6-tetramethyl 2,4 diethyltetrahydropyrimidine and2,4 dimethyl-2,4,6-triethyltetrahydropyrimidine which upon reaction withammonia and hydrogen gives a mixture of 3,5-diamino-3,4-dimethylhexaneand 3,5-diamino-3-methylheptane. This mixture of isomeric diamines maybe termed di(methyl ethyl ketone) diamine.

The epoxy ethers contained in the compositions of the invention have atleast six carbon atoms and one or more ethereal oxygen atoms. In orderthat the composition will cure by reaction with the diamine intomaterial of high molecular weight and resinous character, the epoxyether has a 1,2-epoxy equivalency which is greater than one. By theepoxy equivalency, reference is made to the average number of 1,2-epoxygroups 0 c-) I I contained in the average molecule of the epoxy ether.In the case where a substantially pure, simple compound is used, theepoxy equivalency will be an integer of two or more. For example, theepoxy equivalency of diglycidyl ether or of the diglycidyl ether ofethylene glycol is two while that of the triglycidyl ether of glycerolis three. However, the epoxy ether may be a mixture of chemicalcompounds which, although they are of similar identity and chemicalconstitution, have different molecular weights. The measured molecularweight of the mixture, upon which the epoxy equivalency is dependent,will necessarily be an average molecular weight. Conse quentiy, theepoxy equivalency of the epoxy ether mixture will not necessarily be aninteger of two or more, but will be a value which is greater than one.For example, an epoxy ether particularly suitable for use in theinvention is that made by reacting bis- (4-hydroxyphenyl) -2,2-propanewith epichlorhydrin in alkaline solution at a mol ratio of about 1.4mols of epichlorhydrin per mol of the dihydric phenol. The product is aresinous mixinder a pressure of 500 to 1500 pounds per square so ture ofepoxy ethers having a measured average molecular weight of 791. Analysisshows the product to contain about 0.169 equivalent of epoxy groups per100 grams. Consequently, the product has an epoxy equivalency of about1.34i. e., an average of about 1.34 epoxy per molecule.

The epoxy ethers used in the invention preferably contain only theelements carbon, hy-

drogen and oxygen. They include simple monoing a 1,2-epoxy equivalencygreater than one such as the polyglycidyl ethers of glycerol,diglycerol, erythritol, pentaglycerol, pentraerythritol, mannitol,sorbitol, polyallyl alcohol, polyvinyl alcohol and the like. Thepolyglycidyl polyethers of the polyhydric alcohols are prepared byreacting the polyhydric alcohol with epichlorhydrin in the presence of0.1 to about 2% of an acidacting compound as catalyst such as borontrifluoride, hydrofluoric acid or stannic chloride whereby thechlorhydrin ether is formed as product. The reaction is effected atabout 50 C. to

. 125 C. with the proportions of reactants being such that there isabout one mole of epichlorhydrin for each molecular equivalent ofhydroxyl group in the polyhydric alcohol. Thus in preparing the ether ofdiethylene glycol, which glycol contains two hydroxyl groups in eachmolecule thereof, about two moles of epichlorhydrin for each mole ofdiethylene glycol are used. The resulting chlorhydrin ether from thereaction of a polyhydric alcohol with epichlorhydrin isdehydrochlorinated by heating at about 50 C. to 125 C. with a small, say10%, stoichiometrical excess of a base. For this purpose, sodiumaluminate gives good results.

Preparation of the polyglycidyl ethers of the polyhydric alcohols may beillustrated by considering application of the foregoing method inpreparing the glycidyl ether of glycerol. In parts by weight, about 276partsof glycerol '(3 moles) are mixed with 828 parts of epichlorhydrin(9 moles). To this reaction mixture is added 10 parts of a diethyl ethersolution containing about 4.5% of boron trifluoride. The temperaturerises,

as a result of the exothermic reaction and ex- 0 ol cn-cn aluminate.While agitating, the reaction mixture is heated andrefluxed at 93 C. forabout 9 hours. After cooling to atmospheric temperature, the insolublematerial is filtered from the reaction mixture and low boilingsubstances removed by distillation to a temperature of 205 c at 20 mm.pressure. The epoxy ether, in amount of 261 parts, is a pale yellow,viscous liquid. It has an epoxide value of 0.671 equivalent per 100"grams and the molecular weight is 324 as measured ebulshow that theglycidyl ether has an epoxy equivalency of 2.18-i. e., an average of2.18 epoxide groups per molecule. 4

The 1,2-epoxide value of the glycidyl ether is determined by heating aone gram sample of the ether with an excess of pyridinium chloridedissolved in pyridine (made byadding "pyridine to 16 cc. of concentratedhydrochloric acid to a total volume of one liter) at the boiling pointfor 20 minutes whereby the pyridinium chloride hydrochlorinates theepoxy groups to chlorhydrin groups. The excess pyridinium chloride isthen back titrated with 0.1 N sodium hydroxide to the phenolphthaleinend point. The epoxide value is calculated by considering one HCl asequivalent to one epoxide group. This method is used for obtaining allthe epoxide values discussed herein.

A preferred group of epoxy ethers with which the superior properties ofthe aforementioned diamines react with particular advantage are thoseprepared by reacting a dihydric phenol with epichlorhydrin in alkalinesolution. These products are of resinous character and when used in thecompositions of the invention, enable valuable materials, resistantagainst solvents, to be obtained upon curing with the diamines. Any ofthe various dihydric phenols are used in pre paring these glycidylethers including mononuclear phenols like resorcinol, catechol,hydroquinone, etc., or polynuclear phenols like bis-(4- hydroxyphenyl)-2,2-propane(bis phenol), 4,4- dihydroxy benzophenone, bis-(4-hydroxyphenyl) 1.1-ethane, bis- (4-hydroxyphenyl) -1,1-isobutane,bis- (4-hydroxyphenyl) -2,2-butane, bis (4- hydroxy-Z-methylphenyl)-2,2-propane, bis-(4-hydroxy-2-tertiary butyl phenyl) -2,2-propane, bis-(Z-dihydroxynaphthyl)-methane, 1,5-dihydroxy naphthalene, etc.

The glycidyl ethers of the dihydric phenols are made by heating at C. to150 C. the dihydric phenol with epichlorhydrin, using one to two or moremoles of epichlorhydrin per mol of the (ihydric phenol. Also present isa base such as sodium, potassium, calcium or barium hydroxide in'amountof 10 to 30% stoichiometric excess of the epichlorhydrin-i. e., 1.1 to1.3 equivalents of base per mol of epichlorhydrin. The heating iscontinuedfor several hours to convert the reactant to a tafiy-likeconsistency whereupon the reaction product is washed with water untilfree of base. Although the product is a complex mixture of glycidylethers, the principal product ma be represented by the formula wherein Rrepresents the divalent hydrocarbon radical of the dihydric phenol andnis.-0,"1,12, 3,

etc. The length of the chain can be made to vary by changingithemolecular proportion of epichlorhydrin and dihydric phenol. Thus bydecreasing the mols of epichlorhydrin per mol of. dihydric alcohol fromabout two downwards towards one, the molecular weight and the softeningpoint of the resinous glycidyl ether is increased, In general, theseglycidyl ethers, having an epoxy equivalency between one and two,contain terminal 1,2-epoxy groups, and have alternate aliphatic andaromatic nuclei linked together by ethereal oxygen atoms.

The nature of the glycidyl ethers from dihydric phenols can be betterunderstood by considering loscopically in a dioxane solution. Thesevalues preparation of a particular product which I prefer to use in myinvention. This product will hereinaitei be designated by the term ResinA.

of bis-(4-hydroxyphenyl) -2,2-propane (bis-phe-.

nol) and 5 mols of epichlorhydrin are added to 6.43 mols of sodiumhydroxide as a aqueous solution. While being stirred, the reactionmixture is gradually heated to about 100 C. during 80 minutes time andis maintained at 100-104 C. for an additional 60 minutes under reflux.The aqueous layer is decanted and the resin washed with boiling wateruntil neutral to litmus whereupon the resin is drained and dehydrated byheating to about 150 C.

The resulting resinous glycidyl ether has a softening point of 100 C.'(Durrans Mercury method) and a molecular weight of 1133 measured byboiling point elevation of a dioxane solution. The epoxide value is0.116 equivalent per 100 grams so the epoxide equivalency is 1.32epoxide groups per molecule.

In like manner, other resinous glycidyl ethers of bis-phenol may beprepared which will have different molecular weights depending upOn themolar ratio of epichlorhydrin to dihydric phenol used in preparationthereof. This fact is illustrated by the following table which shows thevariation in properties with variation in the molar ratio.

Mol Ratio Mol Ratio Equiv. Epoxy Epichlor- NaOH to gag EE: Epoxy Groupshydrin to Epichlor- Point weight per per bis-Phenol hydnn 100 gms. M

C'. 2.15 1.1 43 451 0.318 1.30 l. 4 l. 3 84 791 0.169 1.34 1. 33 l. 3 90802 0. 137 l. 10 1 1.25 1.3 100 1,133 0.116 1.32 1.2 1.3 112 1,420 0.0851.21

I Resin A.

These glycidyl ethers from bis-phenol are a complex mixture of compoundsbelieved to have as the principal component thereof a substance whichmay be represented by the formula CH.

equivalents of amino per 100 grams so there is preferably used about 90parts by weight of the diamine with each 100 parts by weight of theether. Likewise, when the glycidyl ether 01' bisphenol is used such asResin A having an epoxy value of about 0.1 6 equivalents of epoxy per100 grams, it is preferred to have the composition contain about 6.7parts by weight of diacetone diamine for each 100 parts of the glycidylether.

While it is particularly preferred to use an.

equivalent amount of the diamine in the compositions so as to havepresent one amino group, per epoxy group, good results with curing toinfusible products are obtained with 60% to 120% of the equivalentamount of the diamine is employed. By varying the diamine from suchpreferred proportions, the fusibility and solubility properties of thereacted product may be regulated and modified. The use of diaminebelowabout 60% or above about 120% of the equivalent amount will tend toreduce the toughness, increase the brittleness and decrease the heatdistortion point of the reaction product. Moreover, the products willgenerally be fusible. In some cases, products of such type aredesirable. There can be used as little as about down to 5% of theequivalent amount of diamine or up to about 300%. Compositionscontaining a large excess of diamine are useful for production offusible and soluble reaction products which find application as chemicalintermediates.

The compositions of the invention are best reacted or cured by heatingat-a temperature of C. to 250 C. Some of the compositions such as thosecontaining the epoxy ether made from glycerol and epichlorhydrin willset up and cure in reasonable times at lower temperatures includingordinary atmospheric temperatures like from 15 C. to 25 C. Othercompositions containing an epoxy ether harving aromatic groups thereinsuch as Resin A,,for example, react very slowly at such lowertemperatures. This is advantageous in the use and application of thepreferred compositions because they are stable for several days time.Consequently, the diamine may be mixed with the epoxy ether and it isnot necessary immediately to apply the composition for the wherein n isO, 1, 2, 3, etc. It may be noted that the observed-molecular weight andepoxy value is probably low due to inherent inaccuracies of the methodsof determining the values. The epoxy value appears to give only about ofthe theoretical value, but in any event the epoxy equivalency is greaterthan one and the resinous glycidyl ethers cure to hard, tough, insolubleand infusible resins upon heating with the diamines used amount thatthere is one primary amino group for each 1,2-epoxy group in the epoxyether. For example, when diglycidyl ether is used with diacetonediamine, the ether has an epoxy value of about 1.54 equivalents of epoxyper 100 grams and the diamine has an amino value of about 1.72-

purpose intended such as protective coatings, molding materials and thelike. When the composition contains the diamine in the preferredproportion, it sets up and cures to a hard, tough product uponapplication of heat. At preferred temperatures of C. to C., the reactionis complete in from about 10 minutes to an hour's time. a

The compositions of the invention containing the preferred proportionsof diamine are particularly useful for protective coatings bydissolving.

in an organic solvent'and applying the solution to a surface withsubsequent curing of the film of resin-forming material. Varioussolvents are suitable for this purpose such as lower saturated ketoneslike acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl hexylketone, cyclohexanone, methyl cyclohexanone, etc.; esters like ethylacetate, isopropyl acetate, butyl acetate, isoamyl acetate, etc.; andmonoalkyl ethers of ethylene glycol like methyl, ethyl or butyl ethers.Preferably such solvents have a boiling pointbelow 175 C. If desired,other materials like lower aromatic hydrocarbons such as benzene,toluene and/or xylene may be used in combination with like.

the oxygen-containing compounds for the purpose of cheapening the costof the solvent.

The solutions of the compositions of the invention are applied forcoating surfaces needed to be protected by brushing, spraying and thelike. The amount of solvent contained in the solution may be varied tosuit the particular need. Ordinarily, thesolution will contain about to60% of the composition of the invention. The

solution is applied to the surface to be coated,

and either the solvent is first allowed toevaporate, after which heat isapplied by circulating hot air or by use of infra-red lamps, or theheating is I efl'ected with simultaneous removal of solvent and curing.

The coated surfaces containing a film of the cured composition have verydesirable properties i and this is especially true when the epoxy etherused in the composition is a glycidyl ether of a dihydric phenol such asResin A, for example.

When cured, the resulting film is resistant to attack by acids such as50% sulfuric acid. The

' aqueous sodium. hydroxide without harm.

When used asfilm-forming agents, the compositions may have various othermaterials incorporated therewith besides solvents such as pigments andother resins. Thus pigments like titanium oxide, antimony oxide, carbonblack,

chrome yellow, zinc oxide, para red, and the like,

may be used. Best results in preparing the enamels are obtained bygrinding the pigment z.

with a portion of the solvent and epoxy ether,

, and then adding the remainder of the solvent' and epoxy ether afterthe grinding operation.

, The enamel is ready for application upon addition of the curing agent,the diamine.

With either varnishes or enamels containing the compositions of theinvention having the diamine in preferred proportions, thick layers ofthe film-forming material may be applied to a surface. Curing completelytherethrough iis attained because the conversion to an in- 1 solublefilm is not dependent upon contact with air. This fact also makes thecompositions valuable in manufacture of laminates wherein the laminaeare cloth, paper, glass-cloth and the Such laminae are impregnated withthe compositions which are ordinarily dissolved in a volatile solventlike acetone. After drying,

and, if desired, partial curing, the impregnated .sheets are stacked andthe cure completed in a press using suflicient pressure to form ahomogeneous and coherent mass for the resin-forming material such as 200to 1000 or more pounds per square inch.

The new compositions possess a peculiar and unexpected property makingthem particularly suitable for molding operations. Most resin- ,formingmaterials contract in volume during curing thereof. In contrast, thecompositions of the invention tend to expand during curing.

Consequently, upon manufacturing molded articles from'the compositionsby introducing the compositions into a mold with application of thecuring heat and'pressure,.the resin-formingmaterial flows and fills themold sharply .so that excellent molded articles are obtained.

ly, di(methyl ethyl ketone) diamine.

ether, is added, the resinous film obtained byspreading the compositionon a glass'panel and baking at 150 C. for 30 minutes is so soft that itmars easily with a finger nail and is brittle so as to tend to chip whenplowed with a knife point rather than giving a coherent ribbon. On theother hand, the film prepared in like manner using a 50% solution ofResin A in methyl ethyl ketone to which 6.5% diacetone diamine based onthe weight ofresin, is added with curing by baking at 150 C. for30-minutes, is so hard that it cannot be scratched or marred with afinger nail and is also tough so as to give a continuous coherent ribbonupon being plowed with the point of a knife. Moreover, a film having thesame hardness and toughness is obtained when 3.8% diacetone diamine issubstituted for the 6.5% diamine. Another composition of the inventionalso gives a hard, tough film. This is prepared by dissolving an equalweight of Resin A in a 50-50 mixture of xylene and monobutyl ether ofethylene glycol, and adding 2.8% of the mixture of diamines describedbefore, name- 'I'he solution is spread on a glass plate, the solventallowed to evaporate, and is then baked at 150 C. for 30 minutes.Besides being hard and tough, this film, like that obtained by curingwith diacetone diamine, adheres tenaciously to the glass.

Theproduct obtained from the composition of the invention has excellenttoughness and hardness so as to provide a useful coating material. Thisis evident from results obtained'with a composition consisting of equalparts by weight of Resin A and a 50-50 mixture of the monobutyl ether ofethylene glycol and xylene to which had been added 4.5% of diacetonediamine based on the weight of the resin. This solution upon applicationto a steel panel with baking for 30 minutes at 150 C. after evaporationof the sol- I vent, gave a cured film having a Sward hardness of 41 anda Taber abrasion of 4.5 mg. per 100 cycles.

As a general observation in the chemical and resin arts, amines arenotorious in giving dark colored products when reacted especially whereapplication of heat is involved. It was surprising to discover thatwhile primary diamines having the amino groups attached to primarycarbon atoms had a marked tendency toward formation of discoloredproducts when used as curing agents for the epoxy ethers, the diaminesused in the present invention which contain at least one primar aminogroup linked to a tertiary 'carbon atom having the unexpectedly superiorproperty of curing the epoxy ether with little or no development ofcolor. Furthermore,

The compositions are not only useful for molding, but also for castingin plaster of Paris, rubher or other molds. Various fillers, dyes, and

' pigments may be incorporated with the composiupon subjecting the curedproducts to prolonged heating, the products from said primary diaminesare prone to develop considerable color while those cured with thediamines used in the invention are relatively resistant to developmentof further discoloration.

These facts may be illustrated by results obtained with enamelscontaining the composition of the invention wherein diacetonediamine ispresent as curing agent in comparison with use of diethylene triaminewhich contains each of the primary amino groups linked to primary carbonatoms. Two groups of enamels were prepared using a different solvent ineach group. In each case, the base was prepared from the ingredientsnoted below by dissolving the resin in the solvent, adding the pigmentand grinding in a ball mill for 28-30 hours. Base I contained one-thirdpart by weight each of Resin A, titanium dioxide pigment, and methylisobutyl ketone. Base II contained 30.8% b weight of Resin A, 30.8% oftitanium dioxide pigment and 38.4% of monomethyl ether of ethyleneglycol. Portions of each base were weighed out and the curing agentnoted in the table below was added, the percentage being based on theamount of Resin A contained therein. The enamels were coated on cleansteel panels which were then baked at 150 C. for 30 minutes. A second'coat was applied in the same manner. The table below gives the results.

using a solvent composed of 60% methyl ethyl ketone, 20% n-butyl acetateand 20% xylene, the diacetone diamine also gave the good white color,but the other two amines gave films which were discolored far more thanwhen the solvent was the mixture of xylene and monobutyl ether of.

ethylene glycol.

Since the presence of the pigment in the cured enamel tends to maskdiscoloration in the resin of the film, unpigmented varnishes wereprepared. Varnish base III was prepared by dissolving an equal amount byweight of Resin A in a solvent consisting of a -50 mixture of xylene andmonobutyl ether of ethyleneglycol. Varnish base IV contained an equalamount of Resin A dissolved in methyl ethyl ketone. To the varnisheswere added the curing agents noted in the 'table below, the percentagebeing based on the weight of the resin in the composition. The filmsWith reference to the foregoing table, the scratch test was performed byplowing a knife point into the cured film. The designation tough is usedto denote a film which gave a continuous tough ribbon, while brittle isused to designate a film which gave a shower of chips. The toluene spottest is a measure of the resistance of the film to solvents and wasperformed by placing a drop of toluene on the cured film withobservation of the efiect thereof after 15 minutes. The color scaleemployed was as follows: The numeral 0 indicates the film was pure whitelike before baking and the numeral 5 indlcates a light ivory color,while intermediate numerals have reference to uniform graded variationstherebetween.

The superior color characteristics obtained with the compositions of theinvention are not confined to enamels containing titanium dioxide aspigment. White enamel bases were prepared using 40.2% by weight ofantimony oxide as pigment, 26.8% of Resin A, and 33% of solvent con-Curing Agent Color of Cured Film 4.0% oiaceione diamine Good whitecolor. 2.33 o ethylene diamine. Intermediate color (of! white). 4%diethylene triamine Light ivory color.

were obtained by flowing the varnishes on glass I panels and curing for30 minutes at C.

Curing Agent (olor oi Cured Film 4.5% diacetone diamine. Colorless. 4%diethylene diamine---- Brown tint. 4.5% diaoetone diamine. Colorless. 4%diethylene triamine Darkest brown tint.

An excellent heat curable enamel containing a composition of theinvention is prepared using equal parts by weight of methyl ethylketone, powdered titanium dioxide pigment and Resin A. To this mixtureis added 1% to 2% by weight of diacetone diamine. The resulting enamelis brushed or sprayed onto surfaces and may be cured to a hard toughwhite film by baking for 10 minutes to one-half hour at 125 C. to 175 C.

The compositions are well suited for manufacture of laminated articles,which operation may be illustrated by laminates of duck cloth. A 50%solution of Resin A in acetone was prepared and 3% of diacetone diamine,based upon the weight of resin, added thereto. Sheets of duck cloth weredipped in the solution and allowed to dry and pre-cure in circulatingair at 105C. for the time noted in the table below. This gave dryimpregnated sheets which were convenient to handle and stack. Four-plylaminates were obtained from the impregnated sheets by stacking andhardening between stainless steel cauls. The hardening was effected byheating for 10 minutes at C. under a pressure of 200 pounds per squareinch. Smooth surfaced laminates of high strength and excellent glosswere obtained. The surface of the laminates was of satisfactory hard-Barcol Hardlimeof Pro-cure 4 minniae 34 6 minutes 40 8 minutes 41 Thecompositions are also useful as adhesives for uniting various objectssuch as wood, paper, resins, or even metal. When a very reactive epoxyether is used in the adhesive such as that from a polyhydric alcohol andepichlorhydrin, the compositions may be used as cold setting glues sincethey set up and cure hard in reasonable times at ordinary atmospherictemperature like from 15 C. to 25 C. If desired, the compositions may beused as adhesives with curing at the elevated temperatures describedhereinbefore. The glue line obtained with either cold-set or hot-setcompositions of the invention is characterized by its very highstrength. For example. an adhesive composition was prepared by mixingequal parts by weight of Resin A and the epoxy ether from glycerol andepichlorhydrin prepared as described hereinbefore. The mixture was aviscous liquid having a viscosity of about 4600 centipoises at 22-23 C.-To the mixture was added 15% by weight of diacetone diamine as curingagent. .The adhesive composition was spread on a one inch square surfaceof each of two carefully cleaned blocks of phenolic resin with the aidof a doctor blade having a clearance of 0.005 inch. The adhesive coatedsurfaces of the blocks were then united and the blocks were placed in aconstant temperature room set at 77 F. The adhesive gelled in 2 hourstime. After 6 days, the blocks were subjected to the block shear test ofthe Army-Navy-Civil Committee on Aircraft Design Criteria: "WoodAircraft Inspection. and Fabrication. ANC-19 (December 20, 1943)discussed in an article by R. C. Rinker' and G. M. Kline, ModernPlastics. vol. 23, D.- 164, 1945. It was found that the cold curedadhesive had a shear strength of 3000 pounds per square inch. This is ahigh value for adhesives. Plywood or oak blocks could not be used in thetest because the adhesive had a higher shear strength than the woodenthemselves.

I claim as my invention:

blocks 1.- A composition of matter comprising an epoxy ether having a1,2-epoxy equivalency greater than one which is devoid of other re- 12hydroxyphenyi) -2,2-propane having a 1,2-epoxy equivalency ofgreater-than one. and 60% to 120% of the equivalent amount of2.4-diamino- I 2-methylpentane.

5. A composition of matter comprising methyl ethyl ketone solution of aglycidyl ether of bis-"(4-hydroxyphenyl)-2,2-propane having a 1 2-epoxyequivalency of greater than one, and 0% to'120% of the equivalent amountof 2.4- diamino-2-methylpentane.

6. A heat curable enamel comprising 1% to 2%- by weight of2,4-diamino-2-methylpentane and equal parts by weight of methyl ethylketone, powdered titanium dioxide pigment and a glycidyl ether ofbis-(4-hydroxy-phenyl) -2,2-

' propane having a 1,2-epoxy equivalency of 1.32

and a Durran's Mercury method softening point of 100 C.

7. A composition of matter comprising a glycidyl ether of glycerolhaving a 1,2-epoxy equivalency greater than one, and 60% to 120% of theequivalent amount of 2-,4-diamino-2- methylpentane.

8. A process for producing a resinous product which comprises reactingan epoxy ether having a 1,2-epoxy equivalency greater than one which isdevoid of other reactive substituents than alcoholic hydroxyl groupswith a saturated aliphatic diamine of the formula CnH2n(NH2)2 activesubstituents than alcoholic hydroxyl j groups, and 5% to 300% of theequivalent amount of a saturated aliphatic diamine' of the formulaCnH2n(NH2)2 whereinn is an integer of at least 4 containing two primaryamino groups, one of which is directly linked to a tertiary carbon atom.

2. A composition of matter comprising an epoxy ether having a 1,2-epoxyequivalency greater than one which is devoid of other reactivesubstituents than alcoholic hydroxyl groups, and 60% to 120% of theequivalent amount of 2,4-diamino-2-methylpentane.

3.. A composition of matter comprising a glycidyl ether ofbis-(4-hydroxyphenyl) -2.2- propane having a 1,2-epoxy equivalencygreater than one, and 60% to 120% of the equivalent amount of2,4-diamino-2-methylpentane;

4. A composition of matter comprising an acetone solution of a glycidylether of bis-(4- wherein n is an integer of at least 4 containing twoprimary amino groups, one of which is linked directly to a tertiarycarbon atom.

9. The resinous product obtained by the process defined in claim v8.

10. A process for producing a resinous product which comprises reactingby heating at 50 C. to 250 C. a glycidyl ether of a dihydric phenolhaving a 1,2-epoxy equivalency between one and two which is devoid ofother reactive substituents than alcoholic hydroxyl groups with 60% toof the equivalent amount of a saturated.

aliphatic diamine of the formula CnHznmmh wherein n is an integer of atleast 4 containing two primary amino groups, one of which is linkeddirectly to a tertiary carbon atom and the other of which is linkeddirectly to a secondary carbon atom.

11. The resinous product obtained by the process defined in claim 10.

12. A process for producing a resinous product which comprises reactingby heating at C. to C. a glycidyl ether of bis-(4-hydroxy-1 phenyl)-2,2-propane having a 1,2-epoxy equivalency betweenone and two with 60%to 120% of the equivalent amount of 2,4-diamino-2- methylpentane.

13. The resinous product obtained by the process defined in claim 12.

' 14. A process for producing a resinous product which comprisesreacting a glycidyl ether of glycerol having a 1,2-epoxy equivalencygreater than one with 2,4-diamino-2-methylpentane.

15. The resinous product obtained by the process defined in claim 14;

THEODORE F. BRADLEY.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Castan June 29, 1948

1. A COMPOSITION OF MATTER COMPRISING AN EPOXY ETHER HAVING A 1,2-EPOXYEQUIVALENCY GREATER THAN ONE WHICH IS DEVOID OF OTHER REACTIVESUBSTITUENTS THAN ALCOHOLIC HYDROXYL GROUPS, AND 5% TO 300% OF THEEQUIVALENT AMOUNT OF A SATURATED ALIPHATIC DIAMINE OF THE FORMULACNH2N(NH2)2 WHEREIN N IS AN INTEGER OF AT LEAST 4 CONTAINING TWO PRIMARYAMINO GROUP, ONE OF WHICH IS DIRECTLY LINKED TO A TERTIARY CARBON ATOM.